TECHNICAL FIELD
[0001] The present invention relates to a polyetherimide porous body which has fine cells,
and is low in relative permittivity and excellent in heat resistance; and a method
for producing the porous body. The polyetherimide porous body of the invention is
useful for, for example, an electrically insulating sheet integrated into, for example,
a motor for automobiles or industries that involves inverter control.
BACKGROUND ART
[0002] A plastic film has a high electrical insulating property, so that such a film has
been hitherto used in components or members for which reliability is required, for
example, electrical appliances or electronic components such as circuit boards or
motors.
[0003] With a reduction in the size of electronic and electrical appliances, and a rise
in the performance thereof, motors for automobiles or industries that have widely
been used recently are motors having a structure that can be inverter-controlled at
a high voltage.
[0004] However, a high surge voltage generated from the inverter produces an effect on the
motors. Thus, their insulator has been required to have a high reliability.
[0005] An example of measures against a surge voltage is, besides an improvement in the
reliability of electrical insulating property, an intentional reduction in the relative
permittivity of the insulator.
[0006] In general, the relative permittivity of plastic materials is determined in accordance
with their molecular skeleton. Thus, as an attempt for reducing the relative permittivity,
a method of modifying the molecular skeleton is supposable. However, even if the molecular
skeleton is modified, a limit is imposed on the reduction in the relative permittivity.
[0007] As other attempts for reducing the relative permittivity, various methods have been
suggested of using the relative permittivity "1" of air, making a plastic material
porous, and controlling the relative permittivity of the porous material in accordance
with the porosity of the material.
[0008] Conventional ordinary methods for producing a porous body are classified into a wet
method, a dry method and others. The dry method is classified into a physical method
and a chemical method.
[0009] A physical method is generally a method of dispersing a low-boiling-point liquid
(foaming agent), such as a chlorofluorocarbon or hydrocarbon liquid, in a polymer,
and then heating the liquid-dispersed polymer, thereby volatilizing the foaming agent
to form cells.
[0010] A chemical method is a method of adding a foaming agent to a polymer, thermally decomposing
the foaming agent to generate a gas, and forming cells by effect of the generated
gas to yield a porous body.
[0011] Furthermore, in recent years, for a porous body small in cell diameter and high in
cell density, a method has been suggested which includes dissolving a gas, such as
nitrogen or carbon dioxide, in a polymer under high pressure, releasing the pressure,
and then heating the gas to a temperature around the glass transition temperature
or softening point of the polymer to form cells.
[0012] Such a foaming method is a method of producing nuclei from a thermodynamically unstable
state, and expanding and growing the nuclei to form cells. The method has an advantage
of yielding a porous body having unprecedented fine pores.
[0013] For example, Patent Document 1 suggests a method of applying the foaming method to
a polyetherimide to produce a foam small in density and large in mechanical strength.
[0014] Moreover, for example, Patent Document 2 suggests that the foaming method is applied
to a styrene-based resin having a syndiotactic structure to yield a foam having a
cell size of 0.1 µm to 20 µm, and this foam is used as an insulator for an electrical
circuit board.
[0015] Furthermore, for example, Patent Document 3 suggests a low-relative permittivity
plastic insulating film which includes a porous plastic material having a porosity
of 10 % by volume or more, and has a heat-resistant temperature of 100 °C or higher
and a relative permittivity of 2.5 or less.
[0016] Additionally, for example, Patent Document 4 suggests a method for producing a porous
body that is characterized in that, from a polymer solution having a microphase-separated
structure in which discontinuous phases having an average diameter less than 10 µm
are dispersed in a polymeric continuous phase, a component constituting the discontinuous
phases is removed by at least one operation selected from evaporation and decomposition,
and an extracting operation, thereby making the polymer porous.
[0017] Such an electrically insulating sheet is folded when integrated into a motor or some
other. However, conventional electrically insulating sheets made of a porous body
have a problem of being easily cracked when folded, so as to be remarkably lowered
in insulation breakdown voltage.
PRIOR ART DOCUMENTS
PATENT DOCUMENTS
SUMMARY OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0019] In light of the above-mentioned problem, the present invention has been made. An
object thereof is to provide a polyetherimide porous body which is low in relative
permittivity and is not easily cracked (or is excellent in cracking resistance) when
folded, and a method for producing the porous body.
MEANS FOR SOLVING THE PROBLEMS
[0020] The invention is related to a polyetherimide porous body (hereinafter, simply referred
to as "porous body"), comprising a polyetherimide crosslinked body, and having a gel
fraction of 10 % or more, an average cell diameter of 8 µm or less, a volume porosity
of 30 % or more, and an insulation breakdown voltage of 30 kV/mm or more.
[0021] The inventors have found out that a porous body low in relative permittivity and
excellent in cracking resistance is obtained by using a polyetherimide crosslinked
body to form the porous body, adjusting the gel fraction of the porous body to 10
% or more, and further making the porous body to have the above-mentioned porous structure.
[0022] If the gel fraction is less than 10 %, the porous body cannot be improved in cracking
resistance. Therefore, the porous body is easily cracked when folded, and is remarkably
lowered in insulation breakdown voltage.
[0023] If the average cell diameter is more than 8 µm, the porous body cannot be improved
in cracking resistance. Therefore, the porous body is easily cracked when folded,
and is remarkably lowered in insulation breakdown voltage. Moreover, the porous body
is not easily lowered in relative permittivity, or is lowered in mechanical strength.
[0024] If the volume porosity is less than 30 %, the porous body is heightened in rigidity,
not to be easily folded. Alternatively, even when folded, the porous body easily returns
to an original shape thereof when external force is taken away therefrom.
[0025] Accordingly, the porous body (electrically insulating sheet) is not easily attached
to a motor or some other device, or the attachment precision is lowered. Moreover,
the porous body is not easily lowered in its relative permittivity.
[0026] When the insulation breakdown voltage is 30 kV/mm or more, the porous body can be
effectively prevented from undergoing insulation breakdown by a surge voltage in the
use of the porous body as an electrically insulating sheet of a motor or some other
device.
[0027] The polyetherimide crosslinked body is preferably a crosslinked body in which a polyetherimide
is crosslinked with a polyamine having two or more amino groups. The use of the polyamine
as a crosslinking agent makes it possible to further improve the porous body in cracking
resistance.
[0028] The porous body preferably has a cracking frequency of 20 % or less, the frequency
being represented by the following equation, and an insulation breakdown voltage retention
of 60 % or more after the porous body has been folded. When the cracking frequency
is 20 % or less and the insulation breakdown voltage retention is 60 % or more, the
porous body can maintain the insulation breakdown voltage thereof at a high level
even when folded.

[0029] The porous body of the present invention is suitably usable for an electrically insulating
sheet for a motor.
[0030] Also, the present invention relates to an electrically insulating laminated sheet
for a motor, which has a sheet member over at least one surface of the polyetherimide
porous body.
[0031] Further, the present invention relates to a method for producing the polyetherimide
porous body, comprising the steps of:
applying, over a substrate, a polymer solution comprising the polyetherimide, a phase-separating
agent that is phase-separable from the polyetherimide, and a polyamine having two
or more amino groups, and drying the applied solution to produce a phase-separated
structure having a microphase-separated structure; and
removing the phase-separating agent from the phase-separated structure to produce
the porous body.
EFFECT OF THE INVENTION
[0032] The porous body of the present invention is excellent in cracking resistance; thus,
the porous body is not remarkably lowered in its insulation breakdown voltage even
when folded. Moreover, the porous body of the invention is formed using a polyetherimide
crosslinked body to have a microporous structure; thus, the porous body has features
of being excellent in heat resistance and insulating property, and further being low
in relative permittivity.
[0033] For this reason, the porous body of the present invention is suitably usable for
an electrically insulating sheet integrated into, for example, a motor for automobiles
or industries that involves inverter control.
MODE FOR CARRYING OUT THE INVENTION
[0034] The polymer used as the raw material of the porous body of the present invention,
that is, the polymer constituting the continuous phase of the microphase-separated
structure is mainly a polyetherimide crosslinked body. As the polyetherimide, any
known species thereof is usable without especial restriction.
[0035] Examples of a commercially available product thereof include trade names "Ultem 1000-1000"
and "Ultem XH-6050" manufactured by SABIC Innovative Plastics. As far as the object
of the present invention is not impaired, for example, the following may be used together
as raw materials of the porous body: polyamide, polycarbonate, polybutylene terephthalate,
polyethylene terephthalate, polyphenylene sulfide, polysulfone, polyethersulfone,
polyetheretherketone, polyamideimide and polyimide.
[0036] As a crosslinking agent for crosslinking the polyetherimide, any known species thereof
is usable without especial restriction. The crosslinking agent is in particular preferably
a polyamine having two or more amino groups. The polyamine is usable without being
especially limited as far as it is a compound through which imide groups of the polyetherimide
are ring-opened to form intermolecular crosslinkages of the polymer.
[0037] Examples of the polyamine include aliphatic polyamines such as iminobispropylamine,
bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, polymethylenediamine, trimethylhexamethylenediamine,
polyetherdiamine, and 1,3-bis(3-aminopropyl)tetramethyldisiloxane; alicyclic polyamines
such as isophoronediamine, menthanediamine, N-aminoethylpiperazine,3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undeca
ne adduct, bis(4-amino-3-methylcyclohexyl)methane, and bis(4-aminocyclohexyl)methane;
and amino-modified silicones. These may be used alone or in the form of a mixture
of two or more thereof.
[0038] The addition amount of the polyamine is preferably an amount permitting the molar
equivalent of its amino groups to be from 0.001 to 2 per molar equivalent of the imide
groups, more preferably an amount permitting that of the amino groups to be from 0.005
to 0.5 per molar equivalent of the imide groups.
[0039] If the molar equivalent of the amino groups is less than 0.001, the ring-opening
reaction of the imide groups does not advance sufficiently to tend not to yield the
target polyetherimide crosslinked body easily.
[0040] Conversely, if the molar equivalent of the amino groups is more than 2, at the time
of mixing the raw materials together, the mixture is gelated so that the mixture is
not easily made into a film form.
[0041] The phase-separating agent is not particularly limited as far as the agent is a component
which constitutes the discontinuous phase of the microphase-separated structure, and
which can form the microphase-separated structure when the above-mentioned polymer
is mixed with this agent and be extracted with an extracting solvent.
[0042] Examples of the phase-separating agent include, for example, polyalkylene glycols
such as polyethylene glycol and polypropylene glycol; those polyalkylene glycols terminated
at one or each end by methyl or terminated at one or each end by (meth)acrylate; urethane
prepolymers; and (meth)acrylate- based compounds such as phenoxypolyethylene glycol
(meth)acrylate, ε-caprolactone (meth)acrylate, trimethylolpropane tri(meth)acrylate,
dipentaerythritol hexa(meth)acrylate, urethane (meth)acrylates, epoxy (meth)acrylates,
and oligoester (meth)acrylates. These phase-separating agents can be used alone or
in combination of two or more thereof.
[0043] The molecular weight of the phase-separating agent is not particularly limited. The
weight-average molecular weight thereof is preferably 10000 or less (for example,
about 100 to 10000), more preferably from 100 to 2000 since an operation of extracting
and removing the agent is easy. If the weight-average molecular weight is less than
100, the agent does not undergo phase-separation easily from the cured body of the
polymer.
[0044] Conversely, if the weight-average molecular weight is more than 10000, the microphase-separated
structure becomes too large or the extraction and removal of the phase-separating
agent from the phase-separated structure is difficult. In many cases, an oligomer
is used as the phase-separating agent.
[0045] The addition amount of the phase-separating agent may be appropriately selected in
accordance with a combination of the phase-separating agent with the above-mentioned
polymer. In order to produce a porous body having an average cell diameter of 8 µm
or less and a volume porosity of 30 % or more, the phase-separating agent is preferably
used in an amount from 20 to 300 parts by weight, more preferably from 30 to 100 parts
by weight for 100 parts by weight of the polymer.
[0046] A polymer solution is prepared by mixing the polymer, the phase-separating agent
and a solvent together. The solvent is, for example, an amide such as N-methyl-2-pyrrolidone,
N,N-dimethylacetamide, or N,N-dimethylformamide.
[0047] The use amount of the solvent is from about 150 to 2000 parts by weight, preferably
from 150 to 400 parts by weight, more preferably from 300 to 350 parts by weight for
100 parts by weight of the polymer.
[0048] An additive other than the phase-separating agent may be added to the polymer solution.
Examples of the additive include a tackifier resin, a flame retardant, an antioxidant,
an inorganic filler, a bubble nucleating agent, a crystal nucleating agent, a thermal
stabilizer, an optical stabilizer, an ultraviolet absorber, a plasticizer, a lubricant,
a pigment, a crosslinking agent, a crosslinking aid, and a silane coupling agent.
[0049] In the method of the present invention for producing a porous body, the polymer solution
is initially applied onto a substrate, and the applied solution is dried to produce
a phase-separated structure (in the form of, for example, a sheet or film) having
a microphase-separated structure.
[0050] The substrate is not particularly limited as long as it has a smooth surface. A continuous
applying method includes, for example, a wire bar method, a kiss coating method, and
a gravure method. The method of applying in a batch system includes, for example,
an applicator method, a wire bar method, and a knife coater method.
[0051] The polymer solution applied onto the substrate is dried to vaporize the solvent
to yield a phase-separated structure in which the phase-separating agent is microphase-separated.
The temperature at which the solvent is vaporized (dried) is not particularly limited.
It is advisable to adjust the temperature appropriately in accordance with the used
solvent species.
[0052] The temperature is usually from 60 °C to 200 °C. The microphase-separated structure
is usually a sea-island structure in which the polymer and the phase-separating agent
are in a sea form and in an island form, respectively.
[0053] The ring-opening and crosslinking reaction between the polyetherimide and the polyamine
advances in the solvent-vaporizing step. It is therefore unnecessary to conduct any
especial treatment for conducting the ring-opening and crosslinking reaction after
the vaporization of the solvent.
[0054] Next, the porous body is prepared by removing the phase-separating agent that was
microphase-separated from the phase-separated structure. In addition, the phase-separated
structure may be previously peeled off from the substrate before removing the phase-separating
agent.
[0055] The method to remove the phase-separating agent from the phase-separated structure
is not particularly limited, but includes preferably a method of extracting the phase-separating
agent with a solvent. It is necessary to use a solvent that is a good solvent for
the phase-separating agent and does not dissolve the polymer, and includes, for example,
water, organic solvents (e.g., toluene, ethanol, ethyl acetate, and heptane), carbon
dioxide fluid (e.g., liquefied carbon dioxide, subcritical carbon dioxide, and supercritical
carbon dioxide).
[0056] The carbon dioxide fluid can remove the phase-separating agent efficiently because
they can easily penetrate into the phase-separated structure. The extraction may be
attained by using water or the organic solvent together with the carbon dioxide fluid.
[0057] In the case of using the carbon dioxide fluid as an extraction solvent, a pressure
vessel is usually used. The pressure vessel that can be use includes, for example,
a batch type pressure vessel and a pressure vessel provided with a pressure-resistant
device for feeding and winding a sheet. The pressure vessel is usually provided with
a carbon dioxide fluid supply means constituted by pump, piping, valve and the like.
[0058] The extraction of the phase-separating agent may be carried out by feeding/discharging
continuously carbon dioxide fluid into/from a pressure vessel in which the phase-separated
structure is placed, or may be carried out in a pressure vessel in a closed system
(in a state where the charged phase-separated structure and carbon dioxide fluid do
not move to the outside of the vessel).
[0059] In the case of using supercritical carbon dioxide and subcritical carbon dioxide,
swelling of the phase-separated structure is promoted and diffusion coefficient of
the insolubilized phase-separating agent is improved, resulting in efficient removal
of the phase-separating agent from the phase-separated structure.
[0060] In the case of using liquefied carbon dioxide, the diffusion coefficient decreases,
but the phase-separating agent is efficiently removed from the phase-separated structure
because of improved permeability of the liquefied carbon dioxide to the phase-separated
structure.
[0061] It is sufficient for the temperature and the pressure when the phase-separating agent
is extracted with the carbon dioxide fluid to permit carbon dioxide to be made into
each of the states (liquid, subcritical or supercritical state). The temperature and
the pressure are usually from 20 °C to 230 °C, and from 7.3 MPa to 100 MPa, respectively,
preferably from 25 °C to 200 °C, and from 10 MPa to 50 MPa, respectively.
[0062] It is necessary to appropriately adjust the extraction time, depending on the temperature
and pressure during extraction, the added amount of the phase-separating agent, and
the thickness of the phase-separated structure, but the extraction time is usually
1 to 15 hours, preferably 2 to 15 hours.
[0063] The extraction method using water or organic solvent includes, for example, a method
of immersing the phase-separated structure in water or organic solvent, a method of
spraying water or organic solvent to the phase-separated structure, and the like.
[0064] From the viewpoint of removal efficiency of the phase-separating agent, such an immersing
method is preferred. In addition, the phase-separating agent can be removed efficiently
by replacing water or an organic solvent over a few times or performing the extraction
with stirring.
[0065] After the production of the porous body by the extraction and removal of the phase-separating
agent, the porous body may be subjected to drying treatment and others.
[0066] The gel fraction of the porous body of the present invention is 10 % or more, preferably
25 % or more, more preferably 60 % or more.
[0067] The porous body of the present invention has an average cell diameter of 8 µm or
less, preferably 0.1 to 5 µm, more preferably 0.1 to 3 µm.
[0068] The volume porosity of the porous body of the present invention is 30 % or more,
preferably 35 % to 80 %, more preferably 40 % to 70 %.
[0069] The insulation breakdown voltage of the porous body of the present invention is 30
kV/mm or more, preferably 40 kV/mm or more. The upper limit of the insulation breakdown
voltage is usually about 200 kV/mm.
[0070] The relative permittivity of the porous body of the present invention is about 1.4
to 2.5, preferably 1.4 to 1.9.
[0071] About the porous body of the present invention, the cracking frequency thereof is
preferably 20 % or less, more preferably 10 % or less, the frequency being represented
by the following equation:

[0072] About the porous body of the present invention, the insulation breakdown voltage
retention is preferably 60 % or more, more preferably 70 % or more after the porous
body is folded.
[0073] The form of the porous body may be appropriately varied in accordance with the usage
thereof. When the form is a sheet or film form, the thickness is usually 1 to 500
µm, preferably 10 to 250 µm, more preferably 30 to 200 µm.
[0074] The porous body of the present invention is suitably usable for an electrically insulating
sheet for a motor.
[0075] The electrically insulating laminated sheet of the present invention for a motor
is a sheet having a sheet member over at least one surface of the electrically insulating
sheet for a motor, which is the porous body.
[0076] The form of the electrically insulating laminated sheet for a motor is not particularly
limited, and may be a sheet or tape form. The electrically insulating laminated sheet
may be punched out into a required form, or may be three-dimensionally bent.
[0077] By fitting the sheet member, the electrically insulating laminated sheet for a motor
is improved in strength and lubricity.
[0078] Examples of the sheet member include a nonwoven fabric, paper and a film. In order
to improve the electrically insulating laminated sheet in heat resistance, it is preferred
to use a nonwoven fabric, paper, or a film having heat resistance.
[0079] The thickness of the sheet member is not particularly limited, and is usually 5 to
100 µm, preferably 5 to 50 µm. If the thickness of the sheet member is less than 5
µm, the sheet member does not easily give strength to the electrically insulating
laminated sheet for a motor.
[0080] If the thickness is more than 100 µm, the power of the motor is lowered by a decline
in the winding number of its coil line, or the electrically insulating laminated sheet
for a motor is not easily made low in relative permittivity.
EXAMPLES
[0081] The present invention will be described below by way of Examples, without intending
to limit the present invention thereto in any way.
Measurement and Evaluation Method
Gel Fraction
[0082] The porous body (0.5 g) was wrapped with a resin film (TEMISH NTF1133, manufactured
by Nitto Denko Corporation), and the wrapped body was put in a container. Thereto
was added about 50 mL of N-methyl-2-pyrrolidone as a solvent. This system was stirred
with a stirrer for 24 hours. Thereafter, the solvent was wiped away from the resin
film.
[0083] The porous body was heated and dried at 240 °C for 3 hours, and then the weight of
the resultant gel body was measured. The gel fraction was calculated out in accordance
with the following expression:

Average Cell Diameter
[0084] The porous body was cooled with liquid nitrogen, and was cut with a cutting tool
perpendicularly to its sheet plane to prepare an evaluation sample. The cut surface
of the sample was subjected to Pd-Pt vapor deposition treatment. The cut surface was
observed with a scanning electron microscope (SEM) ("JSM-6510LV," manufactured by
JEOL Ltd.). An image thereof was binarized with image processing software ("NanoHunter
NS2K-Lt" manufactured by Nanosystem Corporation) to be separated into a cell region
and a resin region.
[0085] The respective maximum horizontal string lengths of the cells were measured. About
40 cells that are cells from a cell having the largest cell diameter to a cell having
the 40
th largest cell diameter, the average value of the cell diameters was calculated out.
The value was defined as the average cell diameter.
Volume Porosity
[0086] The specific gravities of the porous body and non-porous body were measured respectively
with an electronic gravimeter (MD-300S, manufactured by Alfa Mirage Co., Ltd.), and
the volume porosity was calculated from the following equation:

Insulation Breakdown Voltage
[0087] By the method in accordance with the standard as defined in JIS C2110, the insulation
breakdown voltage of the porous body was measured at a pressure rise rate of 1 kV/sec.
Cracking frequency
[0088] From a produced porous body, a sample is cut away which has a size of 25 mm (in the
TD direction) x 50 mm. The sample is folded in half (25 mm x 25 mm). An area of 25
mm x 10 mm in the sample from the resultant folded part is pressed at a pressure of
2 MPa for one second using an oil hydraulic press.
[0089] Thereafter, the total crack length of the folded part of the sample is measured using
an optical microscope (ELIPSE ME600, manufactured by Nikon Corporation) with a magnifying
power of 100 to 500. The cracking frequency (%) is calculated in accordance with the
following equation:

Insulation breakdown voltage retention
[0090] From a produced porous body, a sample is cut away which has a size of 25 mm (in the
TD direction) x 50 mm. The insulation breakdown voltage of the sample is measured
in the same way as described above. A sample having the same size is folded in the
same way as described above.
[0091] The insulation breakdown voltage of the resultant folded part is measured in the
same way as described above. The insulation breakdown voltage retention after the
folding is calculated in accordance with the following equation:

Relative Permittivity
[0092] The relative permittivity was determined by measuring a complex permittivity at a
frequency of 1 GHz by the cavity resonator perturbation method and defining its real
part as the relative permittivity.
[0093] A strip-shaped sample (sample size: 2 mm x 70 mm length) was used for the measurement
with a measurement equipment such as a cylindrical cavity resonator ("Network Analyzer
N5230C", manufactured by Agilent Technologies, Inc.; "Cavity Resonator 1GHz", manufactured
by Kanto Electronic Application and Development Inc.).
Example 1
[0094] To a 1000-mL four-necked flask was added 730 g of N-methyl-2-pyrrolidone (NMP), and
this system was heated to 70 °C. Thereto were added 189 g of a polyetherimide (PEI)
resin (Ultem 1000-1000, manufactured by SABIC Innovative Plastics) and 81 g of a PEI
resin (UltemXH-6050, manufactured by SABIC Innovative Plastics). The resultant system
was stirred for 5 hours to yield a PEI resin solution (I).
[0095] To the resultant PEI resin solution (I) were added polypropylene glycol having a
weight-average molecular weight of 400 in an amount of 45 parts by weight for 100
parts by weight of the PEI resin, and 1,10-decanediamine in an amino group molar equivalent
of 0.04 per molar equivalent of the imide groups of the PEI resin. These components
were stirred to yield a transparent homogenous PEI resin solution (II).
[0096] In a comma direct manner, the PEI resin solution (II) was applied onto a PET film,
and then the applied solution was dried at 130 °C for 8 minutes to vaporize and remove
NMP. Thus, a phase-separated structure having a microphase-separated structure was
produced.
[0097] The phase-separated structure was put in a 30-L pressure-resistant vessel, and then
carbon dioxide was injected thereinto in an atmosphere of 35 °C. The inside thereof
was pressurized to 30 MPa.
[0098] While this pressure was kept, the vessel was kept as it was for 60 minutes. Thereafter,
a carbon dioxide fluid was injected thereinto at a flow rate of about 90 kg/hour until
the total use amount of the fluid became 180 kg, and then the fluid was discharged
to make an operation of extracting the remaining solvent and polypropylene glycol.
[0099] Thereafter, while the atmosphere temperature was set to 85 °C to raise the temperature
of the carbon dioxide fluid, 320 kg of a carbon dioxide fluid was further injected
thereinto and discharged to conduct an extraction treatment. In this way, a PEI porous
body was produced.
Example 2
[0100] A PEI porous body was produced in the same way as in Example 1 except that a dimethylsiloxane
having both terminals each modified with an amine (KF-8010, manufactured by Shin-Etsu
Chemical Co., Ltd.) was added in an amino group molar equivalent of 0.02 per molar
equivalent of the imide groups of the PEI resin instead of the addition of 1,10-decanediamine
in the amino group molar equivalent of 0.04 per molar equivalent of the imide groups
of the PEI resin.
Example 3
[0101] A PEI porous body was produced in the same way as in Example 1 except that a dimethylsiloxane
having side chains partially substituted with phenyl groups and having both terminals
each modified with an amine (X-22-9409, manufactured by Shin-Etsu Chemical Co., Ltd.)
was added in an amino group molar equivalent of 0.02 per molar equivalent of the imide
groups of the PEI resin instead of the addition of 1,10-decanediamine in the amino
group molar equivalent of 0.04 per molar equivalent of the imide groups of the PEI
resin.
Comparative Example 1
[0102] A PEI porous body was produced in the same way as in Example 1 except that 1,10-decanediamine
was not added.
Table 1
|
Example 1 |
Example 2 |
Example 3 |
Comparative Example 1 |
Polyamine species |
1,10-Decanediamine |
KF-8010 |
X-22-9409 |
- |
Molar equivalent (mol) of amino groups per mole of imide groups |
0.04 |
0.02 |
0.02 |
- |
Polypropylene glycol (parts by weight) |
45 |
45 |
45 |
45 |
|
Porous body thickness (µm) |
207 |
189 |
190 |
185 |
Gel fraction (%) |
68 |
93 |
93 |
0 |
Average cell diameter (µm) |
0.24 |
1.7 |
1.7 |
8.8 |
Volume porosity (%) |
54.3 |
50.1 |
49.3 |
43.8 |
Cracking frequency (%) |
4 |
0 |
0 |
100 |
Insulation breakdown voltage (kV/mm) before folding |
74.3 |
41.9 |
48.9 |
28.7 |
Insulation breakdown voltage (kV/mm) after folding |
62.2 |
34.5 |
43.3 |
15.6 |
Insulation breakdown voltage retention (%) |
83.7 |
82.3 |
88.5 |
54.4 |
Relative permittivity |
1.8 |
1.8 |
1.9 |
2.0 |
INDUSTRIAL APPLICABILITY
[0103] The porous body of the invention is useful for an electrically insulating sheet integrated
into, for example, a motor for automobiles or industries that involves inverter control.